CN107078057B - Heat treatment method for single crystal silicon wafer - Google Patents
Heat treatment method for single crystal silicon wafer Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 94
- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 67
- 238000011282 treatment Methods 0.000 claims abstract description 52
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000004151 rapid thermal annealing Methods 0.000 claims description 85
- 239000007789 gas Substances 0.000 claims description 74
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 19
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000005247 gettering Methods 0.000 abstract description 19
- 230000002542 deteriorative effect Effects 0.000 abstract description 10
- 235000012431 wafers Nutrition 0.000 description 91
- 150000004767 nitrides Chemical class 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/322—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/322—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections
- H01L21/3221—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections of silicon bodies, e.g. for gettering
- H01L21/3225—Thermally inducing defects using oxygen present in the silicon body for intrinsic gettering
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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Abstract
The invention provides a heat treatment method of a monocrystalline silicon wafer, which is characterized in that a monocrystalline silicon wafer is subjected to RTA treatment, the monocrystalline silicon wafer with the entire plane being an Nv area or the monocrystalline silicon wafer with the entire plane being the Nv area including an OSF area is arranged in an RTA furnace, NH is contained in the monocrystalline silicon wafer3While supplying the gas into the RTA furnace, with the gas containing less than silicon and NH3After the preliminary heating is performed at the reaction temperature of (3), the supply of the NH content is stopped3And Ar gas is supplied to the reaction chamber, and NH is left3The RTA treatment was started under an Ar gas atmosphere of gas. Therefore, even when a single crystal silicon wafer having an Nv region in its entire plane or a single crystal silicon wafer having an Nv region in its entire plane including an OSF region is processed, gettering capability can be provided without deteriorating TDDB characteristics.
Description
Technical Field
The present invention relates to a heat treatment method of a single crystal silicon wafer.
Background
It is known in the art that Rapid Thermal Annealing (RTA) treatment is performed in order to impart gettering capability to a single crystal silicon wafer. Such an RTA process is widely applied to a silicon single crystal wafer having a Neutral (N) region in its entire plane, in which excess or deficiency of voids, which are crystal defects called crystal vacancies (hereinafter also referred to as Va), and interstitial crystal defects, which are interstitial silicon (hereinafter also referred to as I-Si), is small. More specifically, the RTA process is applied to a wafer including an Ni region having a large amount of I — Si, an Nv region having a large amount of Va, an Nv region having an oxidation-induced stacking fault (OSF) region, and the like in all planes.
As an example of such RTA treatment, patent document 1 discloses a method in which RTA treatment is performed by adding NH to the solution3Forming a nitride film on the surface of the wafer to supply wafer cavities and provide gettering (gettering) capability. However, when the RTA process is performed on a single crystal silicon wafer having an Nv region in its entire plane or a single crystal silicon wafer having an Nv region in its entire plane including an OSF region in this way, the volume of a micro defect (BMD) becomes large depending on the oxygen concentration of the wafer, and the density of the BMD becomes too high, thereby deteriorating the Time-dependent oxide breakdown (TDDB) characteristic.
[ Prior art document ]
Patent document 1: japanese laid-open patent publication No. 2009 and 212537
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for heat-treating a single crystal silicon wafer capable of providing gettering capability without deteriorating TDDB characteristics even when a single crystal silicon wafer having an Nv region in its entire plane or a single crystal silicon wafer having an Nv region including an OSF region in its entire plane is treated.
In order to solve the above-described problems, the present invention provides a method of heat-treating a single crystal silicon wafer, comprising subjecting the single crystal silicon wafer to RTA treatment, disposing the single crystal silicon wafer having Nv areas in its entire plane or the single crystal silicon wafer having Nv areas in its entire plane including OSF areas in an RTA furnace, and introducing NH into the furnace3While supplying the gas into the RTA furnace, to a position not reachedSilicon and NH3After the preliminary heating is performed at the reaction temperature of (3), the supply of the NH content is stopped3And Ar gas is supplied to the reaction chamber, and NH is left3The RTA treatment was started under an Ar gas atmosphere of gas.
According to the heat treatment method, the thickness of the nitride film formed on the surface of the single crystal silicon wafer can be made thinner than that of the conventional method. Therefore, the amount of holes supplied can be suppressed, and even when a single crystal silicon wafer having an Nv region in its entire plane or an Nv region including an OSF region in its entire plane is processed, excessive oxygen precipitation can be prevented from being promoted, and the oxygen precipitates in the surface layer can be prevented from being exposed. Therefore, the gettering capability can be provided without deteriorating the TDDB characteristics.
Also at this time, the RTA treatment is preferably carried out at 1000 to 1275 ℃ for 10 to 30 seconds. When the RTA treatment is performed under such conditions, holes can be easily appropriately injected, and gettering capability can be more reliably provided. But also prevent slippage or heavy metal contamination from the device.
In this case, the preliminary heating is preferably performed at a temperature higher than normal temperature and lower than 600 ℃. When the preheating is performed at this temperature, NH in the furnace3The concentration becomes uniform and the formation of a nitride film during the preliminary heating is more reliably prevented.
In this case, the single crystal silicon wafer is preferably an Nv region having an overall plane of the wafer and an oxygen concentration of 10 to 12ppm, or an Nv region having an overall plane of the wafer including an OSF region and an oxygen concentration of 9 to 11 ppma. The heat treatment method of the present invention is particularly effective in heat treatment of a single crystal silicon wafer having such an oxygen concentration. According to the heat treatment method of the present invention, even in such an oxygen concentration range, both improvement of TDDB properties and provision of gettering ability can be more surely sought.
In addition, in the RTA treatment, the temperature is raised to silicon and NH3NH in RTA furnace at the temperature at which the reaction takes place3The concentration is preferably 0.5 volume% or more and 3 volume% or less. By making NH in RTA furnace3With such a concentration, a nitride film having a uniform film thickness can be formed more reliably in the wafer plane.
As described above, according to the method for heat-treating a single crystal silicon wafer of the present invention, it is possible to provide gettering capability without deteriorating TDDB characteristics even when a single crystal silicon wafer having an Nv region in its entire plane or an Nv region including an OSF region in its entire plane is treated.
Therefore, according to the method for heat-treating a single crystal silicon wafer of the present invention, a Denuded Zone (DZ) in which no crystal defects occur can be formed from the wafer surface to a predetermined depth that becomes a device active region. Further, by an oxygen precipitation heat treatment or the like, a single crystal silicon wafer in which oxygen precipitates to be a gettering side can be formed in the wafer can be obtained.
Drawings
FIG. 1 is a flow chart illustrating a method for thermally processing a single crystal silicon wafer in accordance with one embodiment of the present invention.
Fig. 2 is a schematic view showing a comparison of the thickness of a nitride film formed by the heat treatment method of the present invention and a nitride film formed by a known heat treatment method.
Fig. 3 is a schematic view showing measured values of TDDB (γ mode) of a wafer having Nv regions including OSF regions in its entire plane after heat treatment by the heat treatment method of the first example or the first comparative example.
Fig. 4 is a schematic view showing measured values of BMD density of a wafer having Nv regions including OSF regions in its entire plane after heat treatment by the heat treatment method of the first example or the first comparative example.
Detailed Description
Since the single crystal silicon wafer having Ni region in its entire plane contains NH3Since the formation of BMD is not promoted even by the RTA treatment in the atmosphere, the TDDB characteristics are not deteriorated. On the other hand, as described above, in a single crystal silicon wafer in which the total plane is the Nv region or the total plane is the Nv region including the OSF region, if the oxygen concentration is too high to a certain extent, NH is contained3When RTA treatment is performed in an atmosphere, BMD formation is promoted, oxide precipitates are exposed on the surface layer, and TDDB characteristics deteriorate.
Thus, the present inventors thought of a single crystal silicon wafer having Nv regions in all planes, or a single crystal silicon wafer having Nv regions in all planesA single crystal silicon wafer having an Nv region including an OSF region and containing NH3When RTA treatment is performed in an atmosphere, if the amount of supply of holes can be suppressed by reducing the thickness of the nitride film formed on the wafer surface, gettering capability may be provided without deteriorating TDDB characteristics.
Specifically, it is known in the art that NH is supplied to both the preheat treatment and the RTA treatment3Through which a gas containing NH3The supply of the gas (2) is limited to the preliminary heating, and the temperature is controlled so that the nitride film is not formed during the preliminary heating, and the supply of the gas containing NH is stopped in the subsequent RTA treatment3The supply gas is switched to Ar gas, and NH contained in the RTA furnace can be remained by supplying the gas during the preliminary heating3The gas of (2) forms a thin nitride film, and the present invention has been completed.
That is, the present invention is a heat treatment method for subjecting a silicon single crystal wafer to RTA treatment, wherein a silicon single crystal wafer having an Nv region in its entire plane or a silicon single crystal wafer having an Nv region in its entire plane including an OSF region is placed in an RTA furnace, and NH is contained in the silicon single crystal wafer3While supplying the gas into the RTA furnace, with the gas containing less than silicon and NH3After the preliminary heating is performed at the reaction temperature of (3), the supply of the NH content is stopped3And Ar gas is supplied to the reaction chamber, and NH is left3The RTA treatment was started under an Ar gas atmosphere of gas.
The present invention will be described in detail below, but the present invention is not limited thereto.
FIG. 1 is a flow chart illustrating a method for thermally processing a single crystal silicon wafer in accordance with one embodiment of the present invention.
In the heat treatment method of fig. 1, first, a single crystal silicon wafer having Nv regions in its entire plane or a single crystal silicon wafer having Nv regions in its entire plane including OSF regions is prepared (fig. 1 (a)). Then, the single crystal silicon wafer is placed in an RTA furnace and NH is contained therein3While supplying the gas into the RTA furnace, with the gas containing less than silicon and NH3The reaction temperature of (4) is preliminarily heated (FIG. 1 (b)), and then the supply of the NH content is stopped3And the supply of Ar gas is started (FIG. 1 (c)), and NH remains3The RTA treatment is started in an Ar gas atmosphere of gas ((d) of fig. 1).
In the heat treatment method of the present invention, NH is supplied to the chamber3The gas is preheated by controlling the temperature to be lower than that of silicon and NH3The reaction temperature of (3) is not so high that a nitride film is not formed on the wafer surface before the RTA treatment is performed. And due to the inclusion of NH3The supply of the gas of (2) is limited to the preliminary heating, and the supply of the gas containing NH is stopped when the RTA treatment is performed3And Ar gas is supplied to the RTA furnace, and NH is contained in the RTA furnace3The gas is uniformly diffused in the furnace due to the concentration gradient, so that NH in the furnace3The concentration will decrease. NH content uniformly diffused during heating and high-temperature maintenance in RTA treatment3The gas (nitriding gas) reacts with silicon to form a thin and uniform nitride film. As a result, the NH content is continuously supplied to the entire process (both preheating and RTA treatment) of the flow of the known heat treatment method3The amount of holes injected through the RTA treatment is suppressed, the oxygen precipitation promoting effect is reduced, and the oxygen precipitates in the surface layer are prevented from being exposed.
The present invention is described in further detail below.
[ Single Crystal silicon wafer ]
The silicon single crystal wafer to be subjected to the heat treatment method of the present invention is a silicon single crystal wafer having an Nv region in its entire plane or a silicon single crystal wafer having an Nv region including an OSF region in its entire plane. Such a wafer can be prepared by, for example, cutting it out of a single crystal silicon manufactured by the czochralski method. The wafer in the defective region is supplied with NH if it is subjected to both the preheating and RTA treatments3The conventional heat treatment of the gas (2) deteriorates the TDDB characteristic, but according to the heat treatment method of the present invention, even when such a wafer is processed, the gettering capability can be provided without deteriorating the TDDB characteristic.
Further, in the case of a single crystal silicon wafer, the total surface is an Nv region and the oxygen concentration is 10 to 12ppm, or the total surface is an Nv region including an OSF region and the oxygen concentration is preferably 9 to 11 ppma. The heat treatment method of the present invention is effective particularly for heat treatment of a silicon single crystal wafer having such an oxygen concentration. The BMD density can be formed within a proper range, and the TDDB characteristic can be more reliably prevented from being deteriorated.
In the present invention, "ppma" means "ppma (JEITA)" (JEITA: the conversion factor of japan electronics and information technology industries association is used).
[ preheating ]
Then, the single crystal silicon wafer is arranged in an RTA furnace and NH is contained3While supplying the gas into the RTA furnace, with the gas containing less than silicon and NH3The reaction temperature of (3) is preliminarily heated. At this time, the heating temperature is made lower than the silicon and NH3Or preferably a temperature higher than room temperature and lower than 600 ℃ so that no nitride film is formed on the wafer surface during the preliminary heating.
In the heat treatment method of the present invention, when the heating temperature in the preliminary heating is the temperature as described above, the thickness of the nitride film formed in the RTA treatment, the heating temperature in the preliminary heating, the heating time and the NH-containing content are set to be equal to each other3There is little correlation between the flow rates of the gases. Therefore, the preliminary heating conditions are not particularly limited, and may be, for example, a heating temperature higher than room temperature (about 25 ℃) and 600 ℃ or lower, a heating time of 10 to 60 seconds, and NH-containing3The flow rate of the gas of (4) is 0.1 to 5L/min.
To contain NH3The gas (2) is not particularly limited, but may be suitably used, for example, one containing NH3Ar gas of (4), and the like. As will be described later, in the present invention, the RTA treatment is performed to heat the silicon and NH3NH in RTA furnace at the temperature at which the reaction takes place3The concentration is preferably 0.5 volume% or more and 3 volume% or less. Therefore, with NH content supplied during preheating3NH of gas3Concentration in terms of NH in RTA furnace at the time of RTA treatment3The concentration is preferably within the above range, and more specifically, for example, 1 volume% or more and 6.5 volume% or less.
[ stopping supply of NH-containing gas3Gas and start of Ar gas supply ]
To carry outAfter the preliminary heating, the supply of NH is stopped3Gas and start of supply of Ar gas.
Where the supply of NH is stopped3The gas and the start of the supply of Ar gas may be either or both of them. And, the supply of NH is stopped3The gas and the start of the supply of the Ar gas may be performed before the RTA treatment described later is started, or may be performed simultaneously with the start of the RTA treatment.
[ RTA treatment ]
Then the NH remains3The RTA treatment was started under an Ar gas atmosphere of gas. In addition, the method includes the step of stopping supply of NH3In the heat treatment method of the present invention in the gas step and the step of starting to supply Ar gas, the RTA treatment is performed by heating to silicon and NH3NH in RTA furnace at the temperature at which the reaction takes place3Although the concentration is not limited, particularly, if the concentration is 0.5 vol% or more and 3 vol% or less, the thickness of the formed nitride film can be easily made almost the same even if the conditions such as the temperature and time of the RTA treatment and the flow rate of the Ar gas are different. Therefore, although the RTA treatment conditions are not particularly limited, it is preferable to perform the RTA treatment under conditions of a heating temperature of 1000 to 1275 ℃ and a heating time of 10 to 30 seconds, for example, because the gettering ability can be more reliably provided. But also can prevent slippage and dislocation or heavy metal pollution.
Here, the thickness of the nitride film formed by the known heat treatment method was compared with the thickness of the nitride film formed by the heat treatment method of the present invention, and the results as shown in fig. 2 were obtained. In addition, in the known heat treatment method, NH is supplied at a rate of 210 to 350 ℃ for 10 seconds while supplying 3 volume percent3After preheating Ar gas, NH was supplied at a maximum temperature of 1175 ℃ for 10 seconds at a volume ratio of 33RTA treatment of Ar gas (2). On the other hand, in the heat treatment method of the present invention, after the preliminary heating similar to the known heat treatment method is performed, the supply of the NH-containing gas is stopped3And starting to supply Ar gas while performing RTA treatment at the same temperature and time as in the known heat treatment method.
As shown in fig. 2, it can be understood that the thickness of the nitride film formed by the heat treatment method of the present invention is about 2.4nm and is thinner by about 0.1nm, relative to the thickness of the nitride film formed by the known heat treatment method of 2.5 nm. Since the slight thickness difference of the oxide film greatly affects the amount of hole injection in the RTA process, if the thickness of the nitride film is made thinner by the heat treatment method of the present invention than known, the amount of hole injection can be effectively suppressed, and the formation of oxide precipitates on the wafer surface can be suppressed.
Further, after the inventors of the present application continued their research, it was found that the heat treatment method of the present invention is performed by heating to silicon and NH3NH in RTA furnace at the temperature at which the reaction takes place3The concentration is 0.5 volume% or more and 3 volume% or less, and a nitride film having a uniform thickness in the plane can be formed more reliably. Further, it is known that the film thickness uniformity of the nitride film is greatly related to NH in the RTA furnace in the RTA treatment as described above3Concentration, but has little correlation with other preparatory heating conditions or RTA treatment conditions.
Continuously supplying NH to both the pre-heating and RTA processes3The TDDB characteristics, BMD size and BMD density of the wafers heat-treated by the known heat treatment method of (1) are evaluated, and it is found that if the BMD size is less than 22nm, the BMD density is 3 × 109/cm3TDDB properties are particularly good below, on the other hand, if the BMD density is 5 × 108/cm3Above, further 1 × 109/cm3From the above, it is understood that the wafer after heat treatment has a BMD size of 22nm or less and a BMD density of 1 to 3 × 109/cm3The wafer can have particularly good TDDB characteristics and gettering ability.
According to the heat treatment method of the present invention, since the supply amount of holes can be suppressed and the wafer having the above-described BMD size and BMD density can be obtained, the wafer having particularly excellent TDDB characteristics and gettering ability can be obtained.
As described above, according to the heat treatment method of single crystal silicon of the present invention, the preliminary heating is performedThe temperature is controlled so that the nitride film is not formed, and NH remaining in the RTA furnace is passed during the RTA treatment3The gas is used to form the nitride film, so that the thickness of the nitride film formed on the wafer surface by RTA treatment can be made thinner than that of the known heat treatment method. Therefore, since the supply amount of holes can be suppressed, gettering capability can be provided without deteriorating TDDB characteristics even in a single crystal silicon wafer having an Nv region in its entire plane or a single crystal silicon wafer having an Nv region including an OSF region in its entire plane, which deteriorates TDDB characteristics by a known heat treatment method.
[ example ]
The present invention will be specifically described below with reference to examples, comparative examples and reference examples, but the present invention is not limited thereto.
(Single Crystal silicon wafer)
As the single crystal silicon wafers subjected to the heat treatment in example 1 and comparative example 1, single crystal silicon wafers having Nv regions in their entire planes and having different oxygen concentrations and Nv regions including OSF regions in their entire planes were prepared. In addition, 6.0ppma, 8.0ppma, 9.0ppma, 10.0ppma, 11.0ppma, 12.0ppma, and 14.0ppma are prepared for the oxygen concentration of these wafers, respectively.
[ example 1 ]
The prepared wafer is preheated under the following conditions, and then the supply of NH is stopped3And Ar gas starts to be supplied, while NH remains3Under an Ar gas atmosphere, RTA treatment was performed under the following conditions.
(preparatory heating conditions)
The heat treatment temperature is as follows: below 350 deg.C
And (3) heat treatment time: 10 seconds
Supplying gas: 3 volume percent of NH3Ar gas of (2)
Gas supply amount: 0.6L/min
(RTA treatment conditions)
Heat treatment temperature (maximum temperature): 1175 deg.C
And (3) heat treatment time: 10 seconds
Supplying gas: ar gas
Gas supply amount: 20L/min
NH in RTA furnace3Concentration (heating to silicon and NH)3NH in RTA furnace at the temperature (600 ℃) at which the reaction takes place3Concentration): 0.6 volume percent
[ comparative example 1 ]
The prepared wafer is aligned, preheated under the following conditions, and continuously supplied with NH3The RTA treatment was performed under the following conditions.
(preparatory heating conditions)
The heat treatment temperature is as follows: below 350 deg.C
And (3) heat treatment time: 10 seconds
Supplying gas: 3 volume percent of NH3Ar gas of (2)
Gas supply amount: 0.6L/min
(RTA treatment conditions)
Heat treatment temperature (maximum temperature): 1175 deg.C
And (3) heat treatment time: 10 seconds
Supplying gas: 3 volume percent of NH3Ar gas of (2)
Gas supply amount: 20L/min
NH in RTA furnace3Concentration: 3 percent by volume (continuous feed)
Next, TDDB characteristics and BMD density of the wafer heat-treated by the heat treatment method of example 1 or comparative example 1 were evaluated as follows.
(evaluation of TDDB Properties)
Thickness of gate oxide film: 25nm, electrode area: 4mm2Determination criterion of TDDB (γ mode): at 5C/cm2The TDDB (γ mode) was measured under the above conditions, and evaluated on the following basis.
O: 93% ≦ TDDB (γ mode)
And (delta): 80% and less than or equal to TDDB (gamma mode) < 93%
Gamma rays: TDDB (gamma mode) < 80%
(evaluation of BMD Density)
Oxygen precipitation treatment was performed at 800 ℃/4 hours and 1000 ℃/16 hours, then the wafer was cleaved and etched, the BMD density of the cleaved surface was measured, and the following criteria were evaluated
◎：3×109/cm3BMD Density ≦
○：1×109/cm3BMD density < 3 × 10 ≦9/cm3
△：5×108/cm3BMD density < 1 × 10 ≦9/cm3
Gamma BMD density < 5 × 108/cm3
The evaluation results of the single crystal silicon wafer having Nv regions in all planes are shown in table 1, and the evaluation results of the single crystal silicon wafer having Nv regions in all planes including the OSF region are shown in table 2.
[ Table 1 ]
[ Table 2 ]
Fig. 3 shows a graph obtained from the measured value of TDDB (γ mode) of a wafer whose entire plane is Nv region including OSF region, and fig. 4 shows a graph obtained from the measured value of BMD density, which are heat-treated by the heat treatment method of example 1 or comparative example 1.
[ reference example 1 ]
With respect to the wafers used in the reference examples, unlike example 1 and comparative example 1, monocrystalline silicon wafers having an entire plane of Ni region were prepared, and the oxygen concentrations of the wafers were 6.0ppma, 8.0ppma, 9.0ppma, 10.0ppma, 11.0ppma, 12.0ppma, and 14.0 ppma.
The wafers prepared in alignment were subjected to preliminary heating and subsequent RTA treatment under the same conditions as in example 1 and comparative example 1, and the TDDB characteristics and BMD density of the wafers obtained were evaluated on the same criteria as in example 1, and the results are shown in table 3.
[ Table 3 ]
As shown in tables 1 and 2 and fig. 3 and 4, it was found that the BMD density of the entire material was decreased and the TDDB characteristic was suppressed from deteriorating as compared with the heat treatment method of comparative example 1 while maintaining the BMD density to a degree that the material had gettering ability by the heat treatment method of example 1. Particularly, in a single crystal silicon wafer having an Nv region in the entire plane, a significant improvement in TDDB characteristics is observed for an oxygen concentration of 9 to 11 ppma. The BMD density is particularly good at the oxygen concentration, and good gettering ability can be imparted.
On the other hand, as shown in table 3, even when the preliminary heating and the RTA treatment were performed by any of the methods of example 1 and comparative example 1, the single crystal silicon wafers having Ni regions in their entire planes did not show a large difference in BMD density and TDDB characteristics.
Therefore, it is understood from example 1, comparative example 1 and reference example 1 that the present invention exerts an extremely high effect on the improvement of TDDB characteristics when the object of the heat treatment is a single crystal silicon wafer having an Nv region in the entire plane or a single crystal silicon wafer having an Nv region including an OSF region in the entire plane, like the present invention.
As described above, according to the method for heat-treating a single crystal silicon wafer of the present invention, even a single crystal silicon wafer having an Nv region in its entire plane or a single crystal silicon wafer having an Nv region including an OSF region in its entire plane can be adjusted to an appropriate BMD density without deteriorating TDDB characteristics, and therefore, a single crystal silicon wafer having gettering capability and good TDDB characteristics with a DZ layer secured can be manufactured.
In addition, the present invention is not limited to the foregoing embodiments. The embodiments are illustrative, and those having substantially the same configuration as the technical idea described in the claims of the present invention and achieving the same effects are included in the technical scope of the present invention.
Claims (9)
1. A method for thermally treating a single crystal silicon wafer by subjecting the single crystal silicon wafer to Rapid Thermal Annealing (RTA), characterized in that:
a silicon single crystal wafer having a neutral region with a large number of crystal lattice vacancies on the whole plane or a silicon single crystal wafer having a neutral region with a large number of crystal lattice vacancies on the whole plane including an oxidation-induced stacking fault (OSF) is placed in an RTA furnace, and NH is contained in the RTA furnace3While supplying the gas into the RTA furnace, with the gas containing less than silicon and NH3After the preliminary heating is performed at the reaction temperature of (3), the supply of the NH content is stopped3And Ar gas is supplied to the reaction chamber, and NH is left3The RTA treatment was started under an Ar gas atmosphere of gas.
2. The method according to claim 1, wherein the RTA treatment is performed at 1000 to 1275 ℃ for 10 to 30 seconds.
3. The method for thermally processing a single crystal silicon wafer of claim 1, wherein the preliminary heating is performed at a temperature higher than normal temperature and lower than 600 ℃.
4. The method for thermally processing a single crystal silicon wafer of claim 2, wherein the preliminary heating is performed at a temperature higher than normal temperature and lower than 600 ℃.
5. The method for thermally treating a single crystal silicon wafer according to any one of claims 1 to 4, wherein the single crystal silicon wafer is a neutral region having a large number of crystal lattice vacancies in the entire plane, and has an oxygen concentration of 10 to 12 ppma.
6. The method for thermally treating a single crystal silicon wafer according to any one of claims 1 to 4, wherein the single crystal silicon wafer is a neutral region having a large number of crystal lattice vacancies and an oxygen concentration of 9 to 11ppma in all planes.
7. The method for thermally processing a single crystal silicon wafer of any one of claims 1 to 4, wherein in the RTA treatment,heating to silicon and NH3NH in RTA furnace at the temperature at which the reaction takes place3The concentration is 0.5 volume percent or more and 3 volume percent or less.
8. The method of claim 5, wherein the RTA process is performed by raising the temperature to silicon and NH3NH in RTA furnace at the temperature at which the reaction takes place3The concentration is 0.5 volume percent or more and 3 volume percent or less.
9. The method of claim 6, wherein the RTA process is performed by raising the temperature to silicon and NH3NH in RTA furnace at the temperature at which the reaction takes place3The concentration is 0.5 volume percent or more and 3 volume percent or less.
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| JP2014-238308 | 2014-11-26 | ||
| JP2014238308A JP6100226B2 (en) | 2014-11-26 | 2014-11-26 | Heat treatment method for silicon single crystal wafer |
| PCT/JP2015/004761 WO2016084287A1 (en) | 2014-11-26 | 2015-09-17 | Heat treatment method for silicon single crystal wafer |
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| KR (1) | KR102324432B1 (en) |
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| JP6447351B2 (en) * | 2015-05-08 | 2019-01-09 | 株式会社Sumco | Method for manufacturing silicon epitaxial wafer and silicon epitaxial wafer |
| JP6711320B2 (en) * | 2017-06-26 | 2020-06-17 | 株式会社Sumco | Silicon wafer |
| JP6897598B2 (en) * | 2018-02-16 | 2021-06-30 | 信越半導体株式会社 | Heat treatment method for silicon single crystal wafer |
| KR20210151814A (en) | 2019-04-16 | 2021-12-14 | 신에쯔 한도타이 가부시키가이샤 | Silicon single crystal wafer manufacturing method and silicon single crystal wafer |
| EP3929334A1 (en) * | 2020-06-23 | 2021-12-29 | Siltronic AG | Method for producing semiconductor wafers |
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| WO2016084287A1 (en) | 2016-06-02 |
| JP2016100542A (en) | 2016-05-30 |
| KR20170091593A (en) | 2017-08-09 |
| TW201619455A (en) | 2016-06-01 |
| KR102324432B1 (en) | 2021-11-11 |
| DE112015004850T5 (en) | 2017-08-24 |
| US20170253995A1 (en) | 2017-09-07 |
| JP6100226B2 (en) | 2017-03-22 |
| CN107078057A (en) | 2017-08-18 |
| TWI628320B (en) | 2018-07-01 |
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